Amines via the amination of olefins

ABSTRACT

This invention relates to an improvement in the vapor phase catalytic production of an amine by the reaction of a mixture comprising an olefin having from 2 to 8 carbon atoms and ammonia or ammonia type compound. The improvement which provides for high selectivity to the amine resides in the use of an alumino silicate as the catalyst.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a process for producing amines by the reactionof ammonia or ammonia type compound with an olefin.

2. Description of the Prior Art

The earliest work relating to the manufacture of amines by the aminationof olefins particularly ethylamines by the amination of ethylene,appears to have been done by Teter et al. as noted in U.S. Pat. Nos.2,623,061; 2,479,879; 2,417,892; 2,381,470, 2,658,041; 2,381,709;2,392,107 and 2,398,899. These patents show that ammonia can be made toreact with olefins, e.g. ethylene to produce amine. As noted by othersthrough improvements in the process, substantial quantities ofpolyamines and polyolefins were produced by the Teter et al catalystwhich is a metal supported on a spinel type support, silica anddiatomaceous earth and the like.

Olin et al. in U.S. Pat. Nos. 2,422,631 and 2,422,632, discloses aprocess for producing amines and amides by the reaction of amonounsaturated olefin, carbon monoxide and an amine or ammonia. Thecatalyst used is a combination of a dehydrating and a hydrogenationcatalyst, e.g. nickel and activated alumina, copper and silica gel, etc.

Whitman, U.S. Pat. No. 2,501,556 discloses a liquid phase reaction ofammonia and ethylene in the presence of an alkali metal catalyst to formethylamine.

McClain, U.S. Pat. No. 3,412,158 discloses a gas phase process forproducing primary alkyl amines from low molecular weight olefins andammonia by carrying out the gas phase process in the presence of a noblemetal containing catalyst at temperatures of from 90°-175° C., atpressures of from atmospheric to 2,000 psig.

SUMMARY OF THE INVENTION

This invention relates to an improved process for the preparation ofamines by the vapor phase catalytic reaction of an olefin having from 2to 8 carbon atoms and ammonia or a primary or secondary amine. In thebasic process the olefin is reacted at a temperature and pressuresufficient to effect formation of the amine, but controlled to preventpolymer formation. The improvement generally resides in the use of

(a) a temperature from 200°-450° C.,

(b) a pressure of from 300-6,000 psig and

(c) an alumino silicate, e.g. a zeolite, catalyst.

There are several advantages associated with the invention as comparedto prior art processes. These advantages include:

an ability to produce amines in high selectivity with respect topolyamines, e.g. greater than about 80% without producing substantialby-products, e.g. polymers in the form of polyolefins. The production ofpolymers has been a serious problem with many of the prior artprocesses;

an ability to use a gas phase reaction which permits high productionrate in producing amines;

an ability to reduce the amount of by-product in the form of by-productnitrogen compounds (nitriles) as compared to prior art processes; and

an ability to obtain moderate conversion of olefin to amines by virtueof the use of the particular catalyst and conditions employed.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Olefins having from 2 to 8 carbon atoms in the structure can beconverted by vapor phase amination to the amine. The olefins can be monoor polyunsaturated, e.g. a diene. However, a monounsaturated olefinwhich is an alpha-beta unsaturated aliphatic olefin is preferred.Dienes, particularly conjugated dienes, have a tendancy to polymerize.Examples of olefins suited for producing amines by this process areethylene, propylene, butylene, isobutylene, pentene, hexene,cyclohexene, cyclopentadiene and butadiene, of these the C₂ to C₄olefins are preferred in practicing the invention and these wouldinclude ethylene, propylene, and the butenes.

In the amination of the olefins, and ammonia or an ammonia typecompound, i.e. a primary or secondary amine can be used as the reactant.If one uses a primary or secondary amine as the reaction item, secondaryand tertiary amines are formed as product. Suitable primary andsecondary amines can be represented by the formulas RNH₂ and (R)₂ NHwhere each R is a hydrocarbon group having from 1-6 carbon atoms in thestructure. Examples of amines include methyl amine, dimethylamine, monoan di-n-propylamine, cyclohexylamine and the like. Lower alkyl aminesare preferred.

In the process, an ammonia type compound is reacted with the olefin attemperatures broadly from about 200°-450° C., but preferably attemperatures of about 300°-400° C. Lower temperatures result in lowerconversion and higher temperatures result in lower selectivity whichgenerally appears in the form of polymer or nitrile formation.

Pressures suited for practicing the invention are from about 300-6,000psig with preferred pressures of from about 600-1100 psig. Generally,pressures lower than about 600 psig result in poor conversion of theolefin to amine. On the other hand, as the pressure is increased aboveabout 1500 psig conversion is increased only slightly. However,selectivity to the amine decreases particularly when conjugated dienessuch as butadiene are used as the reactants. In order to minimize therecovery problems associated with separating the amine from thereactants and other by-products, higher conversions can be waived andpressures of from about 600-1100 psig used as this permits extremelyhigh selectivities, e.g. greater than 95%.

Another important variable in the gas phase amination of the olefin isthe mole ratio of ammonia to olefin in the feed. Generally, the moleratio can be from about 0.2-20 moles ammonia per mole of olefin withpreferred ranges of from about 1-4 to 1. Mole ratios higher than about10:1 of course require greater energy expenditure to handle the largerquantities of gas that pass through the reactor, and there seems to beno significant advantage in terms of increased selectivity or conversionat these higher ratios of ammonia to olefin. On the other hand, as theconcentration of ammonia to olefin falls below about 0.2:1, there is aloss of selectivity to the amine.

The gas hourly space velocity (GHSV) which has units of volume of gasper volume of catalyst in unit time i.e. (cc gas at STP)/(cc catalysthours⁻¹). The gas hour space velocity can be from about 500-5,000 with apreferred range being from about 750-2,000. As the space velocity isincreased toward the upper end of the range, conversion generally fallsdramatically, particularly above about 3,000. On the other hand, as thespace velocity approaches the lower level of 500, selectivity decreasesas by-products form. Typically, conversions of from about 3-20% areachieved at space velocities of about 500-3,000.

One of the important factors in achieving the results of highselectivity to amines without the concomitant production of substantialamounts of polymers, e.g. polyethylene or other by-products asencountered in the prior art processes is in the use of aluminosilicates, e.g. various ion exchanged zeolites as the catalyst. Variousions can be incorporated into the synthetic crystalline aluminosilicates which enhance the activity of the resultant catalyst. It isbelieved the acidity of the catalyst as well as the resistance of theion to reduction to the metal form plays an important role in thecatalyst activity and selectivity. The acidity is provided by themetallic ions. The reduction of the metal ions to the metal destroys theacidity and this form then catalyzes the dehydrogenation of the amine tonitriles. Trivalent ions and particularly the rare earth metals, i.e.lanthanum, neodymium, praseodymium, are well suited. Other trivalentions include iron, aluminum, chromium and rhenium. Divalent ions oftenresult in poorer conversion than the rare earth trivalent ions however,selectivity is good. Divalent ions include calcium, magnesium andcopper. Zinc, although a divalent ion, generally effects dehydrogenationof the amine to the nitrile, but it is operable. Monovalent ions, i.e.hydrogen, sodium and ammonium ions are also effective for the catalyst.However, sodium and other alkali metals result in lower conversions thanthe hydrogen form. As is known the hydrogen form can be prepared fromthe ammonium form and for purposes herein is referred to as the hydrogenform. The preferred metal ions for the exchanged zeolites are lanthanumand hydrogen as these provide good yields, good selectivity and goodcatalyst life.

Synthetic crystalline alumino silicates generally are present in thesodium form and, of course, the sodium form can be replaced by washingthe zeolite with a metal salt solution and effecting ion exchange withthe sodium. The hydrogen form can be obtained by washing with an acid oran ammonium salt solution and heating to drive off ammonia.

The term zeolite, as used herein, refers to the synthetic, crystallinealumino silicate of the molecular sieve type. They are formed by thereaction of sodium aluminate and colloidal silica. These zeolites arewell known and are described in U.S. Pat. Nos. 3,130,007; 2,882,244 and3,130,006 and incorporated by reference. These references primarilyrelate to zeolites of the X and Y type, the Y type having a silica toalumina ratio of at least 3.5. Other types such as the A, and mordenitescan also be used in the gas phase amination of olefins described here.Zeolite Y which is described in U.S. Pat. No. 3,130,007 providesexcellent results.

Another form of alumino silicate is silica-alumina where the silicacontent is from about 10-50% by weight. This form of silica-alumina isdistinguished from the zeolite in that it is not in the crystallineform. Generally, conversion is lower with the noncrystallinealumino-silicates than with the zeolite, particularly those exchangedwith a trivalent rare earth metal ion.

The following examples are provided to illustrate preferred embodimentsof the invention and are not intended to restrict the scope thereof.

EXAMPLE 1

The reactor used consisted of a 36 inch tube having an internal diameterof 0.815 inches. A thermowell of one-quarter inch outside diameter wasaxially extended up from the bottom portion of the reactor. The catalystpellets, as specified, occupied the lower half of the reactor. The upperpart of the reactor was filled with inert packing, one-quarter inchunglazed porcelain berl saddles. The saddle served as a preheating andmixing device. Each section of the reactor, i.e. the preheater and thecatalyst bed, was equipped with an external electric heater which wasindependently controlled to maintain temperature.

The reactor product was sampled by diverting the product stream to ascrubber containing an icewater mixture. A material immiscible withwater remained as an upper layer and decanted or was condensed in a dryice-cooled trap. Noncondensibles were measured by a wet test gas meter.The products were then analyzed by vapor-phase chromotography.

Table 1 represents the results of amination of various olefins undervarious conditions, the conditions being specified in the table.Catalyst SK-500 is a pelleted rare earth lanthanum exchanged zeolite Ysold by the Union Carbide Company. G-980 is a silica-alumina catalystcontaining 13-25% alumina.

With respect to amine formation in Table 1, employing a tolueneextraction method of analysis selectivity to monoethylamine was 79% inRun 1, and 68% in run 2, runs 3 and 4 produced an 87-92%monoisopropylamine. Run 5 and 10 resulted in conversions to 100% 2-aminobutane and cyclohexylamine respectively.

Subsequent analysis using distillation techniques indicated about an 80%selectivity to amines instead of the 95-100% level reported in Run 1.The concentration of monoethylamine was about 61%. This trend would beexpected to be carried along in other runs. The toluene extractionmethod may have resulted in lower polymer analysis, however, yielderrors may have resulted in the distillation technique. Nonetheless,both analytical techniques show high selectivity to amines.

                                      TABLE 1                                     __________________________________________________________________________    Amination of Olefins Under Various Operating Conditions                                                                  Sp-Time Yield                                                NH.sub.3 /Olefin                                                                         To Amines                                                                           lb./hr./ft..sup.3                  Run                                                                              Olefin Catalyst                                                                           T,°C.                                                                      Psig                                                                             GHSV                                                                              Mole Ratio                                                                          % Conv.                                                                            % Selec.                                                                            of catalyst                        __________________________________________________________________________    1  Ethylene                                                                             SK-500                                                                             386 3000                                                                             3000                                                                              2.3   13.2  95   13.8                               2  Ethylene                                                                             "    403 "  "   "     20.6  85   18.7                               3  Propylene                                                                            "    367 "  3400                                                                              1.0   6.2   91   15.5                               4  Propylene                                                                            "    383 "  3100                                                                              2.8   8.4   93   10.3                               5  Propylene                                                                            G-980                                                                              446 2000                                                                             3000                                                                              4.1   6.2  100    6.0                               6  Butene-2                                                                             SK-500                                                                             374 2000                                                                             3300                                                                              5.4   3.7  100    3.9                               7  Butene-1                                                                             "    377 2000                                                                             3300                                                                              5.5   5.4  100    5.3                               8  Isobutylene                                                                          "    313 2000                                                                             3100                                                                              2.7   6.5  100   11.1                               9  Isobutylene                                                                          "    278 2000                                                                             2900                                                                              1.3   6.1  100   16.0                               10 Cyclohexene                                                                          "    335 3000                                                                             3000                                                                              4.8   10.0 100   14.3                               11 Propylene                                                                            "    400 4000                                                                             3100                                                                              1.0   8.7   93   20.5                               __________________________________________________________________________

EXAMPLE 2

The procedure of Example 1 run 3 was repeated except for the variationin temperature, pressure and other process conditions as specified inTable 2. The catalyst used was SK-500.

The results show that conversion dropped with decreasing temperature butselectivity to the amine increased. For propylene it wasn't untilreactor temperatures reached about 410° C. that polymerization startedto occur.

                  TABLE 2                                                         ______________________________________                                        Direct Amination of Propylene at 4000 psig Pressure                           Changes in Product Distribution with Temperature                              Temperature, °C.                                                                    413      400      383    360                                     NH.sub.3 /Propylene                                                           (molar ratio)                                                                              0.9      1.0      0.9    0.9                                     Space velocity, hr.sup.-1                                                                  3000     3100     3100   3100                                    Propylene                                                                     Conversion, %                                                                              9.6      8.7      7.8    4.5                                     Selectivity, %                                                                Isopropylamine                                                                             68       88       91     93                                      Unknown      9        7        3      4                                       Diisopropylamine                                                                           4        5        6      3                                       Polymers     19       0        0      0                                       Space-time yields,                                                            lb./hr./cu.ft.                                                                of catalyst                                                                   Isopropylamine                                                                             17.1     19.6     18.9   11.0                                    Diisopropylamine                                                                           0.8      0.9      1.0    0.3                                     TOTAL        17.9     20.5     19.9   11.3                                    ______________________________________                                    

EXAMPLE 3

Another series of amination reactions were carried out using a reactorconsisting of a 316 stainless steel tubing 9 inches long of 3/4" outsidediameter and 1/2" inside diameter. The stainless steel reactor wasmounted inside a close fitting block of Inconel metal which wasinstrumented for temperature control. A thermowell extending axiallythrough the reactor was used to measure reactor temperature.

The catalyst volume for the reactor was approximately 30 cubiccentimeters and the catalyst was held in place by a quartz wool plug.The catalysts were sieved to pass through a U.S. standard sieve size 12but retained on an 18 mesh sieve.

Tables 3 and 4 represents results for various olefins, catalysts andreactor conditions.

Table 3 shows that a hydrogen form of mordenite is effective forproducing monoamines from ethylene and propylene in high yield. Very fewbyproducts are formed at 750 psig and temperatures below about 380° C.As with the previous examples conversion increases with temperature butselectivity decreases at the upper end of the temperature range e.g.400° C. Even so, selectivity is much higher than with the conventionalcatalysts on silica.

As compared to Example 1, amine selectivity is higher. Although adifferent analytical technique was used, the major contribution toincreased selectivity was the use of lower pressures. Olefins are lesssusceptible to polymerization at lower pressures.

                                      TABLE 3                                     __________________________________________________________________________    AMINATION OF ETHYLENE AND PROPYLENE                                                                      NH.sub.3 /Olefin                                                                         % Selectivity                           Run                                                                              Olefin                                                                              Catalyst                                                                             T, °C.                                                                     Psig                                                                             GHSV                                                                              Mole Ratio                                                                          % Conv.                                                                            Mono Amines                                                                          Diamine                                                                            Other                       __________________________________________________________________________    1  Ethylene                                                                            H Mordenite                                                                          340 750                                                                              1960                                                                              3.9:1 3.6  98     2    --                                   Zeolite                                                              2  "     H Mordenite                                                                          350 750                                                                              1960                                                                              3.9:1 4.7  97     3    --                                   Zeolite                                                              3  "     H Mordenite                                                                          360 750                                                                              1960                                                                              3.9:1 7.5  97     3    --                                   Zeolite                                                              4  "     H Mordenite                                                                          370 750                                                                              1960                                                                              3.9:1 9.4  91     8.7  0.3                                  Zeolite                                                              5  "     H Mordenite                                                                          380 750                                                                              1960                                                                              3.9:1 12.6 89     10.4 0.6                                  Zeolite -6                                                                           "   H Mordenite                                                                      390 750   1960 3.9:1  14.0 86 11 3                              Zeolite                                                              7  "     H Mordenite                                                                          400 750                                                                              1960                                                                              3.9:1 14.0 88     --   12                                   Zeolite                                                              8  Propylene                                                                           H Mordenite                                                                          300 750                                                                              1960                                                            Zeolite           4.0:1 3    100    --   --                          9  "     H Mordenite                                                                          310 750                                                                              1960                                                                              4.0:1 4.7  100    --   --                                   Zeolite                                                              10 "     H Mordenite                                                                          320 750                                                                              1960                                                                              4.0:1 6.8  100    --   --                                   Zeolite                                                              11 "     H Mordenite                                                                          330 750                                                                              1960                                                                              4.0:1 9.1  100    --   --                                   Zeolite                                                              12 "     H Mordenite                                                                          340 750                                                                              1960                                                                              4.0:1 11   99     --   --                                   Zeolite                                                              13 "     H Mordenite                                                                          350 750                                                                              1960                                                                              4.0:1 11.3   98.6 --   --                                   Zeolite                                                              __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    AMINATION OF PROPYLENE                                                                                   NH.sub.3 /Olefin                                                                         % Selectivity                           Run                                                                              Olefin                                                                              Catalyst                                                                             T, °C.                                                                     Psig                                                                             GHSV                                                                              Mole Ratio                                                                          % Conv.                                                                            Mono Amines                                                                          Diamine                                                                            Other                       __________________________________________________________________________    1  Propylene                                                                           H Mordentite                                                                         330 750                                                                              2340                                                                              2:1   6.7  94.8   3.6  1.6                         2  "     "      340 750                                                                              2340                                                                              2:1   8.4  93     4.3  2.1                         3  "     "      350 750                                                                              2340                                                                              2:1   8.7  93     3.1  2.4                         4  "     Lanthanum                                                                            340 750                                                                               974                                                                              4:1   13.7 97     1.8  1.2                                  Zeolite Y                                                            5  "     Lanthanum                                                                            350 750                                                                               974                                                                              4:1   13.3 97     --   3                                    Zeolite Y                                                            6  "     Lanthanum                                                                            360 750                                                                               974                                                                              4:1   15   90     --   7.8                                  Zeolite Y                                                            7  "     Lanthanum                                                                            330 750                                                                              1950                                                                              4:1   8    100    --   --                                   Zeolite Y                                                            8  "     Lanthanum                                                                            340 750                                                                              1950                                                                              4:1   11.6 100    --   --                                   Zeolite Y                                                            9  "     Lanthanum                                                                            370 750                                                                              1950                                                                              4:1   14.9 94     1.6  23                                   Zeolite Y                                                            10 "     Lanthanum                                                                            290 1100                                                                             1950                                                                              4:1   1.0  100    --   --                                   Zeolite Y                                                            11 "     Lanthanum                                                                            330 1100                                                                             1950                                                                              4:1   8.04 96.3   2.5  --                                   Zeolite Y                                                            12 "     Lanthanum                                                                            350 1100                                                                             1950                                                                              4:1   10.8 95.5   1.8  --                                   Zeolite Y                                                            __________________________________________________________________________

EXAMPLE 4 EXAMPLE 4

The procedure of Example 3 was repeated except for the changes as noted.

Runs 1 and 2 used a mixture of rare earth metals as the exchange ion.The rare earth metal mixture contained 59% lanthanum, 15% cerium, 7%praseodymium, and 19% neodymium by weight. Further the reactor containedonly 6 cc of catalyst, the reactor being a 3/8 inch O.D. 14 inch I.D.stainless steel tube. Other reactor conditions as noted in the previousexamples remained the same.

Runs 3-7 used a silica-alumina catalyst consisting of 15% silica byweight.

Table 5 gives the operating conditions and results.

                                      TABLE 5                                     __________________________________________________________________________    AMINATION OF PROPYLENE                                                                                   NH.sub.3 /Ethylene                                                                         % Selectivity                         Run                                                                              Olefin                                                                              Catalyst                                                                             T, °C.                                                                     Psig                                                                             GHSV                                                                              Mole Ratio                                                                            % Conv.                                                                            Mono Amines                                                                          Diamine                                                                            Other                     __________________________________________________________________________    1  Propylene                                                                           Rare Earth                                                                           340 750                                                                              1950                                                                              4:1     9.8  97     1.1  --                                 Zeolite Y                                                            2  "     Rare Earth                                                                           350 750                                                                              1950                                                                              4:1     10.9 96     0.8  1.3                                Zeolite Y                                                            3  "     Silica-Alumina                                                                       325 750                                                                              1950                                                                              4:1     0.2  100    --   --                        4  "     "      380 750                                                                              1950                                                                              4:1      1.59                                                                              100    --   --                        5  "     "      400 750                                                                              1950                                                                              4:1     2.8  100    --   --                        6  "     "      430 750                                                                              1950                                                                              4:1     3.7  91     5    --                        7  "     "      450 750                                                                              1950                                                                              4:1     3.2  81     19   --                        __________________________________________________________________________

Runs 1 and 2 show slightly lower conversions and selectivity than thetotal lanthanum exchanged zeolite of Table 4 but it would appear thatany of the rare earth metal ions are effective in combination with thezeolite support to produce amines.

Silica-alumina when used as a catalyst gave poor conversions over thecomplete temperature range. However, selectivity was high.

In Tables 3, 4, and 5 it is shown that a rare earth ion exchangedzeolite, namely a lanthanum exchanged zeolite Y, is more active than theother catalysts in the series. Conversions are 3-4% higher on theaverage under similar conditions and yet there is excellent selectivity.

EXAMPLE 5

The procedure of Example 3 was used except for the change in catalystsand reaction conditions. These are specified in Table 6.

                                      TABLE 6                                     __________________________________________________________________________    AMINATION OF OLEFIN                                                                                        NH.sub.3 /Olefin                                                                         % Selectivity                         Run                                                                              Olefin                                                                              Catalyst T, °C.                                                                     Psig                                                                             GHSV                                                                              Mole Ratio                                                                          % Conv.                                                                            Mono Amines                                                                          Diamine                                                                            Other                     __________________________________________________________________________    1  Isobutylene                                                                         H Mordenite                                                                            300 750                                                                              1960                                                                              3.95:1                                                                              15   72     --   29                        2  "     "        310 750                                                                              1960                                                                              3.95:1                                                                              18   49     --   51                        3  "     "        320 750                                                                              1960                                                                              3.95:1                                                                              23   34     --   65                        4  "     "        310 750                                                                              1960                                                                              3.95:1                                                                              26   24     --   76                                                                MEA                                   5  Ethylene                                                                            Lanthanum                                                                              350 750                                                                              1960                                                                              4:1   3.9  100    --   --                                 Zeolite Y                                                            6  "     Lanthanum                                                                              380 750                                                                              1960                                                                              4:1   9.2  94     6    3                                  Zeolite Y                                                            7  "     Lanthanum                                                                              390 750                                                                              1960                                                                              4:1   11.3 86     7    7                                  Zeolite Y                                                            8  Ethylene                                                                            Na Zeolite Y                                                                           350 750                                                                              1960                                                                              4:1   0.5  100    --   --                        9  "     "        380 750                                                                              1960                                                                              4:1   1.3  100    --   --                        10 "     "        400 750                                                                              1960                                                                              4:1   1.9  78     --   --                        11 Ethylene                                                                            NH.sub.4 Zeolite Y                                                                     380 750                                                                              1960                                                                              4:1   8.8  89     7    3                         12 "     "        385 750                                                                              1960                                                                              4:1   9.3  87     7    6                         13 "     "        390 750                                                                              1960                                                                              4:1   9.9  84     0    7                         14 Ethylene                                                                            Zinc Zeolite Y                                                                         350 750                                                                              1960                                                                              4:1   2.0  11     --   89                        15 Ethylene                                                                            Copper Zeolite Y                                                                       350 750                                                                              1960                                                                              4:1   2.1  100    --   --                        16 "     "        360 750                                                                              1960                                                                              4:1   2.9  94     --   6                         17 "     "        370 750                                                                              1960                                                                              4:1   4.1  88     --   12                        18 Ethylene                                                                            Lanthanum                                                                              350 750                                                                              1960                                                                              4:1   1    100    --   --                                 Zeolite X                                                            19 "     Lanthanum                                                                              380 750                                                                              1960                                                                              4:1   3.0  100    --   --                                 Zeolite X                                                            20 "     Lanthanum                                                                              400 750                                                                              1960                                                                              4:1   5.5  96.5   2.5  --                                 Zeolite X                                                            21 "     Lanthanum                                                                              420 750                                                                              1960                                                                              4:1   8.3  89     4.4    6.4                              Zeolite                                                              __________________________________________________________________________

With respect to Table 6 isobutylene in contrast to butene results in ahigh proportion of t-butyl amine. In addition there appeared to becracking of the molecule which results in a larger percentage ofbyproducts. On this basis alkyl substituted olefins would be expected togive a wider variety of products. For best results, in terms ofselectivity, then the olefin should be a straight chain olefin havingalpha-beta unsaturation.

As to the various ion exchanged zeolite catalysts, the sodium, zinc andcopper form resulted in poorer conversion than the lanthanum ionexchanged or hydrogen exchanged form. However the ammonium form isconverted to the hydrogen form and gives good conversions tomonoethylamine (MEA) with slightly lower selectivity than the lanthanumexchanged zeolite.

What is claimed is:
 1. In a vapor phase catalytic amination process for the production of amines from a reaction mixture comprising an olefin having from 2-8 carbon atoms and a nitrogen compound selected from the group consisting of ammonia and primary and secondary amines at a temperature and pressure sufficient for effecting formation of said amine the improvement which comprises:(a) employing a temperature and pressure sufficient to form said amine, but insufficient for forming substantial polymerization of the olefin; and (b) employing as said catalyst an alumino silicate.
 2. The process of claim 1 wherein said alumino silicate is a synthetic crystalline alumino silicate.
 3. The process of claim 2 wherein said crystalline alumino silicate is ion exchanged with a metal ion or a hydrogen ion.
 4. The process of claim 2 wherein said ion is selected from the group consisting of a trivalent metal ion, copper, and hydrogen.
 5. The process of claim 2 wherein said olefin is a monounsaturated olefin having alpha-beta unsaturation.
 6. The process of claim 5 wherein said primary and secondary amine of said nitrogen compound is a C₁₋₆ alkyl amine or cyclohexylamine.
 7. The process of claim 5 wherein said nitrogen compound is ammonia.
 8. The process of claim 7 wherein the pressure in said amination is from 300-6000 psig.
 9. The process of claim 8 wherein the temperature in said amination is from 200°-450° C.
 10. The process of claim 9 wherein the mole feed ratio of ammonia to olefin is from about 0.2-20:1.
 11. The process of claim 10 wherein said alumino silicate exchanging ion is selected from the group consisting of a trivalent rare earth ion and hydrogen ion.
 12. The process of claim 3 wherein said monounsaturated olefin is a straight chain C₂ -C₄ monounsaturated olefin.
 13. The process of claim 12 wherein the alumino silicate is zeolite Y or a mordenite.
 14. The process of claim 13 wherein said olefin is selected from the group consisting of ethylene and propylene.
 15. The process of claim 14 wherein said temperature is from 300°-400° C. and the pressure is from 600-1100 psig.
 16. The process of claim 15 wherein the mole ratio of ammonia to olefin is from 1-10:1.
 17. The process of claim 16 wherein said metal ion is a lanthanum ion.
 18. The process of claim 3 wherein said olefin is cyclohexene.
 19. The process of claim 18 wherein said crystalline alumino silicate is a zeolite Y or mordenite exchanged with a trivalent rare earth metal ion or hydrogen ion.
 20. The process of claim 19 wherein said temperature is from 200°-400° C., said pressure is from 600-1100 psig and the ammonia to olefin mole ratio is from 1-10:1.
 21. The process of claim 1 wherein said alumino-silicate is an acidic, synthetic alumino silicate.
 22. A method of making amines which comprises contacting a mono-1-olefin having from 2-4 carbon atoms and ammonia in the vapor phase, with an acidic, synthetic crystalline alumino silicate under amination conditions which include a temperature in the range of from about 200° C. to 450° C., a pressure in the range of from about 300 to 1500 psig, a mole ratio of ammonia to olefin of about 1:10 and a gas hourly space velocity of about 500 to
 5000. 23. The method of claim 22 wherein said alumino silicate has acidity provided by rare earth ions or hydrogen ions. 